Dyeing vinyl polymers



Patented Dec. 29, 1942 Karl Heymann',

erican Viscose Corporation,.

Meadville, Pa, assignor to Wilming mn Del., 2. corporation-of DelawareNo Drawing. Application March '3, 1940,- Serial No. 322,846

I 16 Claims.

This invention relates to improvements in methods of dyeing yarns andother shapes comprising materials that are not readily permeable towater. More particularly, the invention relates to improvements inmethods of dyeing yarns and other shapes comprising vinyl polymers, suchas polymers of vinyl chloride and copolymers of vinyl acetate and vinylchloride.

This application is a continuation in part of my application SerialNumber 311,109, filed December 27, 1939.

Materials that are not readily permeable to water can not besatisfactorily dyed by the ordinary dyeing procedure used in dyeingcotton, wool, natural silk and regenerated cellulose. When ordinarymethods of dyeing are attempted the dye either does not penetrate thematerial and no dyeing is effected or when dyeing is effected the coloris not fast and leaches out.

'Yarns and other shapes of cellulose acetate which are not readilypermeable to water have been dyed when treated with a liquid swellingagent, such as alcohol, acetone or acetic acid. I'he swelling agentforms or opens pores in the material into which the dye penetrates.There are certain objections to the useof liquid swelling agents.Generally a large amount of swelling agent is required. Also theswelling agent has a tendency to weaken the yarn or shape.

I have discovered that yarns and other shapes comprising vinyl polymers,such as polymers of vinyl chloride and copolymers of vinyl acetate andvinyl chloride can be successfully dyed with suspension dyestufis whenthe dyeing operation is carried out in the presence of suspensions ofcertain normally solid organic compounds which have a solubility inpolymers of vinyl chloride and copolymers of vinyl acetate and vinylchloride of 2% or greater under the conditions at which the dyeing iscarried out. By the term suspension dyestufis is meant dyestufis of thetype applicable to persion (insoluble anthraquinone and azo dyes)sometimes referred to as dispersol dyes, and the dyestuffs referred tohereinafter in the examples cellulose acetate from a disby their tradenames,

are of this type. The com-- pounds which are referred to as assistantsinclude Diphenyl Naphthalene Phenanthrene p-Aminodiphen 1 Y N,N-diphenylethyl carbam ate b-Naphthonitrile -Chlorobenzaldehydel-dimethoxybenzaldehyde P,-

hyde. I o-Hydroxyacetophenone Benzophenone -Hy1droxybenz0phenone etyl-b-naphthylketone Camphor Benzalacetone Anisalacetone BenzcylacetoneIn carrying out my Benzalacetoplienone l-hydroxy-2-acetonaphthone-Methoxybenzophenone enzil Diphenyltriketone Dibenzoylmethanellesoxybenzoin Dimethylaminobenzalde- Benzl1 drol Pheny benz lcarbinolFluoren l a coh b,b'-Dip enoxydlethylether fl-Methoxydi henyl enzyl-anapthylether b-Na hthylmethylether p-Me hoxybenzopnenone Benzoic anhydrideimproved method of dyeing a suspension of a single assistant or severalassistants together may be used. The assistant is, for example,dissolved in a suitable solvent, such as alcohol, and the assistant insolution and a suitable dispersing agent,

such as that known in the trade as IgeponT, are added to the dye bath.

The dye bath containsv a suspension dyestufi. The assistant isprecipitated in the dye bath in colloidal or very finely divided form.When .amino compounds are used as assistants they may be dissolved in anacid solution and precipitated and dispersed in an alkaline dye bath.Phenols may be dissolved in an alkaline solution and precipitated anddispersed in an acid dye bath. Satisconditions when the phenol solutionis added to the dye'bath and is not dispersed. The yarn or shape to bedyed is treated with the dye bath containing the assistant in theordinary vmanner. This procedure may be followed using variousquantities of dyestufl and assistants with different dye bath ratiosandtemperatures of the dye baths depending upon the character of thematerial being dyed and the type of dyeing that is being carried out. Asatisfactory procedure is one in which the dye bath ratio is 1:30 andcontains 1.5% suspension dyestuff with or less of assistant based on theweight of the yarn or shape to be dyed. A suitable dye bath temperatureis about 50 C. and the duration of the dyeing operation one hour. Othertemperatures may also be used.

My invention may also be carried out by applying the assistant fromsuspension directly to the yarn or shape. When the yarn or shape isthere after immersed in the dye bath the assistant aids the action ofthe dye bath on the yarn or shape in the same manner as when it has beenadded to the dye bath.

Instead of using either of the above methods, I may add the assistantdirectly to the vinyl polymers before the yarn or shape is formed. Theyarn or shape containing the assistant is treated with the dye bath inthe ordinary manner.

The following examples are illustrative of the invention:

Example 1.-Yarns comprising copolymers of vinyl acetate and vinylchloride were dyed in dye baths having a dye bath ratio of 1:30 andcontaining 1.5% suspension dyestuff and 5% b- Naphthol based on theweight of the yarn. The temperatures of the dye baths were 60 C. and theduration of the dyeing operation one hour. The dyestufls that were usedwere Cibacete Orange 2R Cibacete Scarlet G Acele Violet B Acele Yellow3G A dye bath was also used with Cibacete Scarlet G 1% and Acele Violetb 1 as the dyestufi.

Example 2.Yarns comprising copolymers of vinyl acetate and vinylchloride were dyed in dye baths having a dye bath ratio of 1:30 andcontaining 1.5% suspension dyestuff and 5% b-Dimethylamino-benzaldehydebased on the weight of the yarn. The temperatures of the dye baths were60 C. and the duration of the dyeing operation one hour. The dyestuffsthat were used were Celliton Red Violet RR Pha'acyl Navy Blue PVPhenacyl Red R Celutate Brill. Blue B Cibacete Rubine BS Artisil DirectYellow 3GP Example 3.Yarns comprising copolymers of vinyl acetate andvinyl chloride were dyed in dye baths having a dye bath ratio or 1:30and containing 1.5% suspension dyestufi and 1.5% Benzophenone based onthe weight of the yarn. The temperatures of the dye baths were 60 C.

' factory results are also obtained under certain and the duration ofthe dyeingcperation tee 1": I I

hour. The dyestufls that were used were Celliton Fast Pink BA AceleScarlet G Calconese Orange 3RC Cibacete Violet B Celutate Fast Blue GLArtisil Direct Yellow 3G ex. Phenacyl Red R Example 4.Yarns comprisingcopolymers of vinyl acetate and vinv1 chloride were dyed in dye bathshaving a dye bath ratio of 1:30 and containing 1.5% suspension dyestufiand 5% o-hydroxydiphenyl based on the weight of the yarn. Thetemperatures of the dye baths were 60 C. and the duration of the dyeingoperation one hour. The dyestufis that were used were Celliton Pink RFCelliton Red BP Celliton Orange '3RN Cibacete Yellow 2RN Celliton FastYellow GRA Cibacete Yellow 5G Cibacete Brill. Blue BGG Celliton FastBlue FFRS Celliton Discharge Violet B Cibacete Discharge Violet 5RCamacyl Brill. Green B Phenacyl Red R Cibacete Violet B Artisil DirectYellow 3GP ex. cone. Celliton Fast Brown 5RA Example 5.Yarns comprisingcopolymers 0! vinyl acetate and vinyl chloride were treated with a bathin a ratio of 1:30 containing 5% o-hydroxydiphenyl based on the weightof the yarn at a temperature of 60 C. and for a period of one-half hour.The yarns so treated were then dyed by immersing in dye baths having adye bath ratio of 1:30 and containing 1.5% suspension dyestufi based onthe weight or the yarn. The temperatures of the dye baths were 60 C. andthe duration of the dyeing operation one hour. The dyestufis that wereused were Camacyl Brill. Green B Phenacyl Red R Cibacete Violet BArtisil Direct Yellow 3GP ex. conc. Celliton East Brown 5RA Whilepreferred assistants and procedures have been shown it is to beunderstood that changes and variations may be made without departingfrom the spirit and scope or the invention as defined in the appendedclaims.

What I claim is:

1. A method. of dyeing yarns and other shapes sisting of benzhydrol,phenylbenzylcarbinol and yl alcohol.

Vinyl Po y ers, comprising the step v aeoasso yestufl in of treating theyarn or shape with a dye bath containing a suspension dyestuil' and anorganic compound selected from the group consisting oi. benzhydrol,phenylbenzylcarbinol and iluorenyl alcohoi i. A method of dyeing yarnsand other shapes comprising copclymers of vinyl acetate and vinylchloride, comprising the step of treating the yarn orshape with a dyebath containing a suspension dyestufi and an organic compound selectedfrom the group consisting of henzhydrol, phenylbenzylcarbinol andfluorenyl alcohol.

5. A method of dyeing yarns and other shapes comprising vinyl polymers,comprising the step of treating the yarn or shape with a dye bath con-'taining a suspension dyestuii in the presence or henzhydrol.

6. A method of dyeing yarns and other shapes comprising vinyl polymers,comprising the step of treating the yarn or shape with a dye bathcontaining a suspension dyestufi in the presence.

9. A method of dyeing yarns and other shapes comprising copolymers ofvinyl acetate and vinyl chloride, comprising the step or treating theyarn or shape with a dye bathcontaining a suspension the resence ofphenylbenzylcerbinol. 10. A method of dyeing yarns and other shapescomprising cop lymers of vinyl acetate and vinyl chloride, comprisingthe step of treating the yarn or shape with a dye bath containing asuspension dyestufi in the presence of fluorenyl alcohol.

ll. A method of dyeing yarns and other shapes comprising vinyl polymers,comprising the step of treating the yarn or shape with a dye bathcontaining a suspension dyestufi and henzhydrol. 12. A method of dyeingyarns and other shapes comprising vinyl polymers, comprising the step oftreating the yarn or shape with a dye hath containing a suspensiondyestuii and phenyloenzylcarbinol.

13. A method of dyeing yarns and other shapes comprising vinyl polymers,comprising the step of treating the yarn or shape with a dye loathcontaining a suspension dyestufl and fluorenyl alcohol. v

14. A method of dyeing yarns and other shapes comprising copolymers ofvinyl acetate and vinyl chloride, comprising the step or treating theyarn or shape with a dye bath containing a suspension dyestuff andbenzhydrol.

15. A method of dyeing yarns and other shapes comprising copolymers ofvinyl acetate and vinyl chloride, comprising the step of treating theyarn or shape with a dye bath containing a suspension dyestuff andphenylbenzylcarbinol.

16. A method of dyeing yarns and other shapes comprising copolymers ofvinyl acetate and vinyl chloride, comprising the step of treating theyarn or shape with a dye bath containing a suspension dyestufl? andfluorenyl alcohol.

KARL HEYMANN.

